Sumitomo Chemical Co., Ltd.

Basic Chemicals Research Laboratory

Trends and Future of

Monomer- MMA Technologies

Koichi N AGAI
Toshiaki U I

MMA production is one of the core businesses of the Basic Chemicals Sector of Sumitomo Chemical, and its
demand and capacity is continuously going to be expanded, mainly in Asia. Now five technologies for monomerMMA production coexist in the world, and none of them is the predominant process. Among those technologies,
the C4 methods are going to be adopted in many production plants. Sumitomo Chemical also selected this technology for its MMA production. In this paper, the current processes, mainly for C4 methods, and the next generation of potential technologies will be reviewed.

This paper is translated from R&D Report, SUMITOMO KAGAKU, vol. 2004-II.

Asia
N. America
Europe
Other
Total Demand
Total Supply

2000

Polymethyl methacrylate (PMMA) can be considful of synthetic resins. Making use of its superior transparency, weather resistance and other characteristics,
the demand for its use in signboards and displays,
lighting equipments, automotive parts, construction
related materials and the like has increased. Recently,
we have seen a rapid expansion in new fields related to

Regional Demand/103t y 1

ered the queen of resins, because it is the most beauti1500

3500

3000

1000

2500

500

2000

1500

IT, making even greater use of its optical characteris-

Total Demand & Supply/103t y 1

Introduction

monomers of these resins, but also there is a demand

for comonomers in fields such as coatings, adhesives
and plastic modifiers. In addition, higher esters like

Fig. 1

07
20

06
20

05

04

20

uses for methyl methacrylate (MMA), in the form of

20

20

sion plates for flat panel displays. Not only are there

03

tics, for example in light-guiding plates and light diffu-

Forecast world MMA demand and supply

(estimated by Sumitomo Chemical Methacrylates Division).

butyl-ester produced by esterification of methacrylic

acid (MAA), which is an intermediate in MMA synthesis, or by transesterification of MMA, are used in a variety of applications.

Asia, especially in China.

In this article, we will comment on the trends in
MMA production technologies. It is usual in bulk

MMA production is one of the core businesses of the

chemicals production that the one or two most compet-

Basic Chemicals Sector of Sumitomo Chemical Co.,

itive methods will survive, but there is a special situa-

Ltd., and we are actively expanding these operations in

tion in MMA production, where five methods currently

Asia, where the demand for monomers and polymers is

coexist. Furthermore, in contrast to the fact that in

increasing rapidly. The world demand for MMA is

Europe and the U.S. the most extended method is the

growing steadily, and it exceeded 2.3 million tons in

traditional acetone cyanohydrin (ACH) process as

2003. Fig. 1 shows the demand and supply predictions

shown in Fig. 2, other methods are already dominant

estimated by the Sumitomo Chemical Methacrylates

in Japan and Asia. Most of these new methods have

Division. A great amount of growth will be expected in

been developed in Japan.

SUMITOMO KAGAKU 2004-II

Trends and Future of Monomer-MMA Technologies

1200

1937. In Japan, Asahi Glass Co., Ltd. and Fujikura

Kasei Co., Ltd. started production in 1938. After that,

DOE: Direct Oxidative Esterification

1000

Capacity/103t y 1

developed and commercialized the ACH process in

C4 Direct Oxdn
C4 DOE
C2 BASF
New ACH
ACH

the ACH method was actually the only industrial production method for MMA for 45 years until Mitsubishi
Rayon Co., Ltd. and Nippon Shokubai independently

800

commercialized the direct oxidation method in 1982.

The raw materials for the ACH process are acetone and

600

hydrogen cyanide. With the sudden rise and develop400

ment of petrochemistry following World War II, it was

possible to obtain acetone as a byproduct of phenol and

200

hydrogen cyanide as well as from acrylonitrile production. In this way, there is an aspect of concerted develer
th
O

07
a
As
i

20

04
a

20

Ja
pa
n

As
i

e
op
Eu
r

.A
m

er

ic
a

Fig. 2

opment along with these products. Sumitomo Chemical also entered the MMA business after introduction

World MMA capacity and technologies

(2004).

of the Sohio acrylonitrile process.

However, with the increase in demand for MMA and
with the changes in the worlds way of looking at indus-

Sumitomo Chemical has commercialized a direct

trial activity in terms of pollution problems and the like,

isobutylene oxidation method in cooperation with Nip-

important weaknesses in the conventional ACH

pon Shokubai Co., Ltd. This was introduced in the

method were revealed, and there was a strong demand

journal SUMITOMO KAGAKU in 1992,1) and this arti-

for changing the production method. The first weak-

cle is a continuation of that one. The Sumitomo Chemi-

ness of the ACH method is the difficulty of acquiring

cal / Nippon Shokubai technology has expanded to

the cyanide. In Japan in particular, almost all of the

five plants, including plants in Korea and Singapore,

cyanide raw material for ACH is the byproduct of the

and another plant is being constructed. Moreover,

Sohio acrylonitrile process, and for conventional Japan-

plans for further expansion are also progressing.

ese makers who produced only several ten thousands

Table 1 shows the history of Sumitomo Chemicals

of tons MMA per year, cyanide synthesis on purpose

MMA operations.

could not be feasible. The second weakness of the

ACH method is processing the waste acid originated
from the use of sulfuric acid. The ACH process pro-

Table 1

History of MMA in Sumitomo Chemical.

duces a large volume of ammonium bisulfate contaminated with organic materials as a byproduct. At one

1962

Start to research on C4 direct oxidation

1964

Introduction of SOHIO acrylonitrile (Niihama)

time, there were cases of this waste acid being dis-

1967

Introduction of MMA polymer (Sumipex) from ICI

posed of in the ocean. In addition, it is said that deep

1967

Start production of monomer-MMA (ACH process)

well processing, the name for disposing of something

1982

Semicommercial C4 Direct Oxidation by Nippon Shokubai (Himeji)

1982

Foundation of Japan Methacryl Monomer (J/V with Nippon Shokubai)

1984

Start JMM Niihama plant

ed in the U.S. and other places. Since these methods

1889

Start JMM Himeji plant

are no longer permissible, recovery as ammonium sul-

1993

Start LGMMA plant (Korea)

fate with addition of ammonia, or recovery as sulfuric

1998

Start SMM plant (Singapore)

2002

Business exchange Acrylic acid and MMA with Nippon Shokubai

2003

Start LGMMA 2nd plant

2005

Scheduled start SMM 2nd plant

deep in the earth without processing it, has been adopt-

acid by investing in facilities for super corrosion resistant materials, as well as a need for large amounts of
energy, is becoming a large financial burden.
In Europe and the U.S., it can be assumed that there
has been little progress in changing the production

History of MMA Production

method because there are large plants for which the

costs are feasible even if hydrogen cyanide is produced

Methacrylic resin is old, having been introduced to

by synthesis, and since the pressure on waste acid

the world by Rohm & Haas in the 1930s. Then, ICI

treatment has not been intense. However, the situation

SUMITOMO KAGAKU 2004-II

Trends and Future of Monomer-MMA Technologies

in Japan is as described above, thus all MMA makers

have converted to their own new methods, even

DuPont Rohm & Haas(DE)

ICI

though there are some companies retaining some ACH

processing.

Degussa
ICI

Table 2 lists the capacities and production methods

for six Japanese MMA producers. In addition, there

The history of their rearrangements and capacities is

shown in Fig.

3.2)

Orkem

Rohm & Haas(US)

Atochem

monomer polymer polymer monomer

merger of polymer

purchase
Ineos

AtoHaas

Cytex

100%

have been repeated alliances and ruptures among

Western MMA makers, and now there are four groups.

Rohm & Haas(US)

business exchange

name change

R & H withdrawal
50%
Roehm

Lucite
560kt/y

R&H
360kt/y

50%
Cyro

100%

Atofina
250kt/y

Atoglas (polymer)

375kt/y

Table 2

Fig. 3

Japanese MMA makers.

Capacity
Remarks
103 t/y

Company, Group

Technology

Mitsubishi Rayon

ACH

107

C4 DO*

110

Thai MMA (MRC45%)

C4 DO

70

China

C4 DO

(90)

C4 DO

90

Korea, LGMMA (SC25%, NS25%)

C4 DO

100

Singapore, SMM (SC100%)

C4 DO

53

C4 DOE**

100

ACH

65

Sumitomo Chemical (Nippon Shokubai)

Asahi Kasei
Kuraray

C4 DO

Mitsui Chemical

Korea, Honam Petrochemical (licence) C4 DO

Mitsubishi Gas Chemical

New ACH

20
20

2004 +15 debottleneck

2006 start
(NS 18)

Methyl methacrylate or methacrylic acid are simple

molecules, but many routes have actually been thought
up for making them from even simpler molecules, and
Besides the routes described below, there are many for
which patent applications have been made as variations

) Kyodo Momomer

40
51

**C4DOE: Isobutylene Direct Oxidative Esterification

Process

MMA Synthesis Routes

a variety of raw materials, C1 through C4, are used.

2005 +80 increase

*C4DO: Isobutylene Direct Oxidation

Table 3

Relations between Western MMA makers.

and possible routes. We will describe the routes that

are already commercialized and those that were once
commercialized. We will also discuss processes for
which there have been announcements of future commercialization and the isobutane process, which has

MMA production technologies.

Raw materials

Feature, Issue

Important catalytic reaction

Maker

Industrialized

(without methanol)
Acetone

Supply of HCN

HCN, H2SO4

Waste treatment

C4 Direct

Isobutylene

2 step oxidation and

1st oxidation; Mo-Bi

Oxidation

(TBA)

esterification

2nd oxidation; Mo-P

Isobutylene

Via methacrylonitrile

NH3, H2SO4

Waste treatment

Isobutylene

Oxidative esterification of

1st oxidation; Mo-Bi

(TBA)

methacrolein

Oxidative esterification; Pd-Pb

Acetone

HCN recycle

Amidation; MnO2

(HCN)

Not use H2SO4

Esterification; NaOMe

HCOOCH3

Too many steps

Dehydration; Zeolite

Ethylene

Use two C1 compounds

Condensation; Amine

CO, H2, HCHO

Via propionaldehide

Oxidation; Mo-P

Alpha

Ethylene

Use two C1 compounds

Carbonylation; Pd complex

Process

CO, HCHO

Via methylpropionate

Condensation; Cs/SiO2

Propyne

Propyne, CO

Isobutane

Isobutane

ACH

MAN
C4 DOE*

New ACH

C2 BASF

Yield 99%
Lack of resource
1 step oxidation

1937

Ammoxidation; Mo-Bi

Carbonylation; Pd complex
Oxidation; Mo-P

Mitsubishi Rayon
Sumitomo/Nippon
Mitsui/Kuraray

1982

Asahi Kasei

19841999

Asahi Kasei

1999

Mitsubishi Gas Chemical

1997

BASF

1989

Lucite

Plan (2008)

Shell (Lucite)

Not yet
Not yet

*DOE: Direct Oxidative Esterification

SUMITOMO KAGAKU 2004-II

Trends and Future of Monomer-MMA Technologies

the greatest expectations for the future.

Direct oxidation processes have as their raw materi-

Naturally, there are strict quality requirements for

als isobutylene or tert-butyl alcohol (TBA), and MMA

MMA, but it is a bulk chemical that is popular for swap-

is produced by esterification of methacrylic acid

ping. Since it is not a product that gets added value

(MAA), which is obtained by a two-step oxidation reac-

from product function or quality, the only point motivat-

tion.

ing the comparison and investigation of various process-

It has already been 20 years since the isobutylene

es is the production at the lowest cost. The cost can be

direct oxidation process was commercialized. It was

calculated from variable costs for the main raw materi-

independently developed by three groups in Japan; Mit-

als (price and amount), steam, electric energy and the

subishi Rayon, Japan Methacryl Monomer (Sumitomo

like, and fixed costs focusing on the cost of facilities.

Chemical and Nippon Shokubai) and Kyodo Monomer

However, the price of the raw materials normally varies

(Kuraray and Mitsui Chemicals), and all three groups

by location, and it varies greatly according to whether

not only have domestic plants, but also have progressed

the company has to purchase the raw materials or pro-

overseas with plants in South Korea (Sumitomo Chemi-

duces them itself. It is difficult to accurately estimate

cal / Nippon Shokubai, Kuraray / Mitsui), Singapore

facilities costs and the amount of steam, secondary raw

(Sumitomo Chemical / Nippon Shokubai) and Thailand

materials, catalysts and the like unless one is involved

(Mitsubishi Rayon). Mitsubishi Rayon is constructing a

in the process development. For example, there are fre-

plant in China. It can be assumed that this proves that,

quently minute amounts of byproducts that must not be

at least based on new construction in Asia, this method

in the product, and a large amount of energy being

is clearly superior to the ACH process economically.

required to separate them out. Each company has its

The reaction routes for the three processes are basical-

own situation concerning this point, and it is difficult to

ly the same, but while the Sumitomo Chemical / Nip-

accurately compare and evaluate the processes without

pon Shokubai method has isobutylene as raw material,

knowing the prerequisite conditions. Therefore, this

the Mitsubishi Rayon and Kuraray / Mitsui Chemicals

article will only cover the general characteristics of each

have TBA. Furthermore, while the Sumitomo Chemical

production method and a qualitative evaluation.

/ Nippon Shokubai method is a two-step direct combi-

Simple profiles of the various production technolo-

nation, the Mitsubishi Rayon method differs in separat-

gies are brought together in Table 3. Most of the

ing methacrolein from a gas produced in the first step

development effort for all of the technologies is spent

and afterwards carrying out the second oxidation reac-

in catalyst development, but reviews focusing on cata-

tion. Comparatively detailed reports have been pub-

lyst techynology
processes 7), 8)

3) 6)

and descriptions focusing on

lished on Japan Methacrylic Monomer and Mitsubishi

Rayon.10) 12)

have already appeared.

As will be discussed later, the Asahi Kasei Corp.

methacrylonitrile (MAN) method and the direct oxida-

Industrialized processes

tive esterification process have TBA as the raw materi1. ACH Process

al. However, isobutylene is contained in the C4 stream

at ethylene plants or cracked gasoline plants (FCC),

leading to a situation where the technology for separatHCN

base

CN

H2SO4

O CH3OH

NH2H2SO4

OH

ing it had to be developed at the same time as the

MMA process. Since the boiling points of isobutylene

and 1-butene in the C4 stream are similar, it is difficult

The ACH process is the predominant method in

to separate them by distillation. All the companies

Europe and the U.S., but as it is a technology from the

developed processes for reaction and separation that

past, we will not discuss it in this article.7) 9)

used catalyst technology. Sumitomo Chemical obtains

high purity isobutylene using a method that works via

2. Direct Oxidation Process

methyl tert-butyl ether (MTBE). This method is also

effective when one wants to obtain the high purity 1-

O2

O2
O

Mo-Bi

Mo-P

acid
OH

SUMITOMO KAGAKU 2004-II

butene used in LLDPE comonomers. This was made

CH3OH
O

practical through the development of a highly selective,

long-life, unique solid catalyst as the decomposition cat-

Trends and Future of Monomer-MMA Technologies

alyst for MTBE, in which silica was impregnated with a

water equal to that of isobutylene always generated

metal sulfate and heat-treated. The Mitsubishi Rayon

with TBA, but also a small amount of water is normally

and Asahi Kasei processes are methods that have a

included in the TBA raw material in connection with

strong acidic ion exchange resin and a heteropolyacid

purification. Thus, there are differences with the

aqueous solution, respectively, as the catalyst, and

isobutylene process in terms of the nature of the first

selectively hydrate the isobutylene in the C4 stream for

step reaction and the input and release of energy. How-

synthesis and separation as TBA. The Asahi Kasei

ever, since it can be assumed that the energy for pro-

method of using a concentrated aqueous heteropoly-

ducing TBA is less than the energy for producing

acid solution is unique from the standpoint of catalyst

isobutylene, this difference may compensate the addi-

technology.14)

tional energy required for the TBA dehydrogenation to

After the commercialization of direct oxidation meth-

isobutylene.

ods, there was a sudden expansion in the demand for

In addition, there is a large difference in the process

MTBE as a gasoline additive, so that the byproducts of

makeup between the Sumitomo Chemical / Nippon

naphtha cracker, FCC and the Oxirane process (propy-

Shokubai first and second step direct combination (tan-

lene oxide) were insufficient. Therefore, dehydrogena-

dem method), and the Mitsubishi Rayon methacrolein

tion of isobutane in C4LPG has come to be carried out

separation method (separation method). Fig. 415) and

on a large scale. The fact that MTBE exists in large

Fig. 516) show the oxidation processes for both. From

quantities as a product means that there is a possibility

the standpoints of facilities and energy, the tandem

for acquiring the raw material for the direct oxidation

process anywhere in the world, but in turn, since its
Purge

cost moves with the price of expensive gasoline, it is

hard to purchase as a MMA raw material, and this can

Incinerator

be thought of as one reason that the C4 direct oxidation

H2O

process has not disseminated to Europe and the U.S.

MTBE has been related to well water contamination
due to leakage from underground gasoline tanks in the
U.S., and starting with California, various states prohibited it, with the U.S. prohibiting it several years later.
This should not immediately spread to Europe, but
(Japanese oil companies abolished it voluntarily) the
U.S. was the largest consumer of MTBE, so its influence will be great. Since there is a worldwide excess in

i-C4
Air
Steam

Extraction

1st Reactor

Fig. 4

2nd Reactor

MAL Absorber
Scrubber
MAL Stripper

Tandem C4 direct oxidation process15).

facilities for MTBE, we can think that there will be a

trend toward easily acquiring raw materials for Sumitomo Chemical / Nippon Shokubai with their process

Purge

that uses decomposition of MTBE.

Incinerator

When Sumitomo Chemical / Nippon Shokubai uses

isobutylene as the raw material, the first step reaction
is somewhat different from the methods of Mitsubishi
Rayon and Kuraray / Mitsui Chemicals that use TBA.
Being able to use TBA in the same manner as isobutylene is due to the fact that it easily breaks down into
isobutylene and water at high temperatures on the
first step catalyst. This reaction is endothermic, and
since the inlet catalyst does not work effectively as a
methacrolein synthesis catalyst, an inexpensive decomposition catalyst such as alumina can be used. In addition, since the first step reaction is possible under
anhydrous conditions, not only is a number of moles of

SUMITOMO KAGAKU 2004-II

i-C4
Air
Steam

Air

Extraction

1st Reactor MAL Absorber 2nd Reactor

Scrubber
MAL Stripper MAA Scrubber

Fig. 5

Separate C4 direct oxidation process 16).

Trends and Future of Monomer-MMA Technologies

method is advantageous. With the separation method,

acid with an anion structure known as the Keggin

the equipment for methacrolein recovery is not only

structure of [PMo 12 O 40 ] 3 . It has uniformly strong

large and complicated, but also needs the energy for it.

Broensted acidity because of the presence of protons

In addition, the air required must be separated for the

as paired cations and suitable oxidation strength origi-

first and second steps, and excess power and preheat-

nating in Mo. Free 12-molybdophosphoric acid

ing are applied. On the other hand, the separation

(H3PMo12O40nH2O) itself does not exhibit such a good

method is advantageous in terms of reaction. The gas

yield, and as a fatal defect, its thermal stability is poor

generated in the first stage is supplied directly to the

and the structure breaks down, so the catalyst life is

second step in the tandem method, so the unreacted

short. It was found early on that forming a heteropoly-

isobutylene and high boiling point byproducts are

acid with a configuration where some Mo atoms are

brought to the second step without alteration. Since

replaced with V, and a crystal structure with a salt

isobutylene, in particular, inhibits the second step reac-

structure where some protons are replaced with alkali

tion, the first step conversion must be as high as possi-

metals was effective for the yield and life. It was

ble. Since the reaction in the second step is inhibited

brought to the level of a practical catalyst by control-

by isobutylene and the byproducts, and there is a limit

ling the addition of other minute components, surface

to the methacrolein concentration, a large reaction ves-

area and the volume of micropores.

sel is necessary for the tandem method, and there are

However, the level of the second step catalyst perfor-

many restrictions compared with the separation

mance is not at all satisfactory yet. Compared with

method. With the tandem method, the requirements

acrylic acid, the selectivity is insufficient, and if the con-

for catalyst performance can be said to be strict, but

version is raised it gets worse. Since the activity is

the problem has been solved by Sumitomo Chemical /

insufficient and there is a problem with the life, the pro-

Nippon Shokubai using a first step catalyst that has an

ductivity per unit catalyst is low. This is one major rea-

extremely high conversion rate without lowering the

son for the isobutylene direct oxidation process not

yield, and a tough, long-life second step catalyst that

having established a firm position as that of the direct

exhibits sufficient capacity even in the presence of poi-

propylene oxidation process for acrylic acid. Therefore,

sonous materials.

a great effort, including that by Sumitomo Chemical, is

The heart of the direct oxidation process is the cat-

continuing to be put into improving the performance.

alytic two-step oxidation reaction. This reaction is simi-

Many patents have been issued regarding catalyst com-

lar to the synthesis of acrylic acid by direct oxidation of

position, and P and Mo are necessary, but almost every

propylene. Our research into direct oxidation of

element in the periodic table has been claimed as an

isobutylene started at about the same time as that for

additive. However, there have been investigations

propylene oxidation, but commercialization was ten

recently into catalyst preparation methods such as

years later than acrylic acid. The fact is that it was that

additives, molding methods, forming and calcination.

difficult to develop the catalysts. The first step catalyst

Sumitomo Chemical has developed good catalysts with

is a Mo-Bi multi component composite oxide catalyst

superior durability using its own catalyst preparation

similar to that for propylene oxidation. In contrast, the

methods, and it has been possible to achieve good pro-

catalyst developed for the second step is a PMo het-

ductivity. Catalysts that not only increase yields but

eropolyacid catalyst with a structure that differs from

also improve the work rate through increased life and

the Mo-V catalyst for acrolein oxidation.

can handle increased production due to increasing

The first step catalyst is a Mo-Bi-Fe-Co/Ni-A (A: alkali metal, alkaline earth, Tl) composite oxide, and is sim-

loads have great merits recently with the strong

demand for MMA.

ilar to that for propylene oxidation. However, as the

Efforts toward further improvements are also contin-

reactivity of isobutylene is different from that of propy-

uing at present for processes such as for example acry-

lene, if a propylene oxidation catalyst is used as is, the

lonitrile and ethylene oxide, which have been already

activity would be too high, with progression to com-

completed, and if we consider the fact that compared

plete oxidation and low yield. This was optimized for

with the first commercialization time, the performance

isobutylene by increasing the amount of alkali metal

has assuredly improved, we can assume that efforts

additive.

toward steady improvements in performance in the

The second step catalyst is based on a heteropoly-

SUMITOMO KAGAKU 2004-II

future will be indispensable for the relatively new

Trends and Future of Monomer-MMA Technologies

process of direct oxidation to survive as a competitive

this can be basically assumed to be a competitive

MMA production method.

method. There are many inquiries from overseas, and

there has been a joint F/S announcement with a company in Taiwan, but no specific plan has been

3. MAN Process

announced yet.
NH3/O2
Mo-Bi

H2SO4

CN

Asahi Kasei discovered that this reaction progresses

CH3OH

O
O

NH2H2SO4

selectively and well with a Pd-Pb catalyst, but investigations into this method were frozen temporarily with the
commercialization of the MAN method. It was neces-

Asahi Kasei developed a route through methacry-

sary to overcome the problems of productivity, byprod-

lonitrile, using isobutylene (TBA in fact) as raw mate-

ucts and catalyst life for commercialization, but with

rial and commercialized it in

1984.19)

Acrylonitrile is

ingenuity in precision synthesis of intermetallic com-

produced in large quantities by the ammoxidation of

pound catalysts, carriers and catalyst supporting meth-

propylene known as the Sohio process, but it is also

ods, and breakthroughs such as the use of a reductive

possible to convert isobutylene to methacrylonitrile

oxidation reaction environment with a lower partial

through a similar catalytic reaction. Asahi Kasei devel-

pressure for oxygen, it could be built up commercially

oped a catalyst for this reaction by modifying an acry-

with success.

lonitrile catalyst, based on existing patents, with a

The merits of this method compared with the direct

similar yield to that of acrolonitrile. In addition, the

oxidation method allow lower facilities costs, because

hydration and esterification processes that follow are

the second stage gas phase oxidation can be eliminat-

similar to the ACH method, and since the yield is

ed and the total yield is high. On the other hand, the

high, it can be assumed that the yield from isobuty-

collection of methacrolein, recycling of excess

lene is superior to that of direct oxidation. However,

methanol, separation of byproducts and the like can be

the disadvantage of using ammonia as a secondary

assumed to require a large amount of energy. It

raw material is a large waste, and as with the ACH

appears that there is a problem of the yield dropping

process, the production of ammonium bisulfate can-

when trying to raise productivity and reducing the

not be avoided. Because of these problems, Asahi

excess methanol to reduce recycling. We can assume

Kasei developed the direct oxidative esterification

that selectivity does not exceed the 95% stated in the

process that will be discussed next and changed the

patents. In addition, since the direct oxidation process

production to the new method in 1999.

is carried out at high-temperature in gas phase, the

reaction heat is recovered almost completely. It is

4. Direct Oxidative Esterification Process

highly possible that most of the reaction heat in the

liquid phase reaction at 100C or less is wasted. It is
said that the life of the catalyst for the later step oxida-

CH3OH/O2

O2

O
Mo-Bi

Pd-Pb
O

tive esterification reaction is sufficiently long, but the

initial investment is very large, and the trends in the
price of Pd may affect the adoption of this method.

Asahi Kasei developed and commercialized the

Even with these problems, among the methods being

method known as the direct oxidative esterification

used, the direct oxidative esterification process is the

process as one that uses TBA as the raw material but

greatest rival technology for the direct oxidation, and

does not produce ammonium bisulfate as a byproduct.

we can assume that it will be necessary to follow the

The first step reaction is the same as direct oxidation,

trends in the future.

and methacrolein is obtained from gas phase oxidation

of TBA. In the later step, oxidative esterification of the

5. New ACH Process

methacrolein is carried out in a liquid catalytic reaction

in methanol to obtain MMA directly.20), 21) Not only are
CN

ammonia and sulfuric acid unnecessary, but there is a

reduction of processes compared with direct oxidation.
Since the yield is higher than that of direct oxidation,

SUMITOMO KAGAKU 2004-II

OH

H2O
MnO2

Na methoxide

OH O

OH NH2
HCOOCH3 HCONH2

H2O

Faujasite

HCN

Trends and Future of Monomer-MMA Technologies

The problems for the conventional ACH process

BASF location, and in terms of the BASF circum-

were the problems in the cyanide supply and with large

stances, it can be assumed that they wanted not only

quantities of ammonium bisulfate byproducts. Howev-

MMA but also higher esters, so the method of taking

er, Mitsubishi Gas Chemical Co., Inc. developed a new

this out as methacrylic acid was used. Therefore, it is

ACH process that solves these two problems and com-

difficult for this to become a general MMA production

mercialized it in

1997. 22)

method, and subsequently there has been no

First of all, the reaction

announcement of more new facilities.

hydrates ACH using a catalyst based on manganese

oxide that does not use sulfuric acid, making -hydroxyisobutyramide, and next forming methyl -hydroxy-

Other processes in development

isobutyrate by means of an amide ester substitution

1. Alpha Process

reaction using methyl formate. Sodium methoxide is

used in this catalyst. This methyl formate becomes formamide, generating hydrogen cyanide in the formate

CO/CH3OH

dehydration, which is recycled and used in the ACH

Pd complex

synthesis process. MMA is made through a dehydra-

O
O

HCHO
O

Cs/SiO2
O

tion reaction with methyl -hydroxyisobutyrate. The

For a long time, many companies have investigated

two dehydration reactions are carried out in the gas

the route through propionic acid or methyl propionate

phase using solid catalysts.

This process solves the cyanide problem and waste

with ethylene as raw material, but recently Lucite estab-

problem of the ACH process with an admirable course

lished this method as the alpha process and is currently

of action, but there are a large number of reaction

carrying out pilot tests. It has been announced that it

steps, and since each step requires separation and

will be commercialized by around 2008.24)

purification, increased consumption of energy cannot

Propionic acid has already been commercialized, but

be avoided. In addition, the comparatively specialized

the alpha process newly employs a process for directly

intermediate methyl formate is required, which is pro-

synthesizing methyl propionate from ethylene,

duced at a special site of Mitsubishi Gas Chemical, so a

methanol and CO. MMA is obtained through gas phase

business in this process could be started.

condensation of methyl propionate and formaldehyde.

It is a simple process for deriving MMA in a two-step
reaction from C2 ethylene. Because of the development

6. BASF Process

of a Pd complex catalyst, the methyl propionate synthesis progresses substantially quantitatively. The condenCO/H2
Co complex

O HCHO
Amine

O2
Mo-P

O CH3OH
acid
OH

O
O

sation process that follows is the key to its practical

application. The reaction occurs in the gas phase, and a
Cs/SiO2 solid base catalyst is used for the catalyst.

One of the MMA production methods that uses eth-

These catalysts have been studied for a long time by

ylene as a raw material was developed by BASF, and a

Amoco and Mitsubishi Rayon, but while both have a

plant that produces 40,000 t/y of MMA along with

high selectivity of 80 90%, the reactivity is not greater

1989.23)

The

than 20 30% in a single pass. In addition, it is said that

reaction of propionaldehyde and formaldehyde is an

there is a problem with catalyst life, and just how far

almost completely quantitative reaction carried out in a

the catalyst performance can be improved is extremely

tubular reactor in the presence of a secondary amine

interesting.

5,000 t/y of methacrylic acid was built in

and acid. The processes after methacrylic acid synthe-

The economics of the process are largely controlled

sis are the same as for the isobutylene direct oxidation

by the raw material situation, but the raw materials

process, and the BASF oxidation catalyst is a het-

necessary for this process are ethylene, CO, methanol

eropolyacid similar to those developed by various

and formaldehyde. All of them are general-purpose raw

Japanese companies. BASF already had propionalde-

materials that are produced in large quantities, but it is

hyde and formaldehyde, and the new construction was

difficult to say if the alpha process, which must pur-

for the methacrolein synthesis process onward. This is

chase all of them on a market price basis, is better than

a production method suited to the conditions of the

the direct oxidation process or the ACH process. If

SUMITOMO KAGAKU 2004-II

Trends and Future of Monomer-MMA Technologies

there is a location that has inexpensive ethylene and

All of the methods discussed up to the present have

large methanol and formaldehyde plants, the circum-

unsaturated hydrocarbons as the raw material, but we

stances probably change greatly.

will focus on a method that uses isobutane as the raw

material and obtains methacrylic acid in a single step.
Unsaturated hydrocarbons, which are the raw materi-

2. Propyne Process

als for petrochemistry, are made by investing a large

amount of energy in saturated hydrocarbons, natural

CO/CH3OH

Pd complex

raw materials. For example, to produce 1 kg of ethylene from naphtha, approximately 20 MJ of energy are

required, and approximately 0.4 kg are necessary per

The propyne process developed by Shell is an

hydrocarbon fuel calculations. The basic situation for

extremely fascinating process that produces MMA with

isobutylene is the same. If direct synthesis of MAA

a yield of 99% in a one step reaction. The production of

from isobutane (separated from C4LPG), which is an

acrylic acid by carbonylation of acetylene (Reppe

upstream resource, was possible, it can be assumed

process) has been replaced with direct oxidation of

that a process that is advantageous in terms of energy

propylene, and BASF has already shut down its last

and economics could be obtained, and effort is being

plant. However, for propyne the yield was insufficient

put into its development.

with a reaction system similar to that for acrylic acid

Rohm & Haas discovered that this reaction pro-

synthesis. Shell found that this reaction progressed

gresses with a heteropolyacid catalyst composed of

with a good yield with a system made up of palladium

Mo-P-Sb-O,28) and after that Asahi Kasei, Sumitomo

acetate, organic phosphine and a protonic acid. For

Chemical and Mitsubishi Rayon and others discovered

example, a system using 2,6-bis (diphenylphosphine)

that with a heteropolyacid catalyst similar to the cur-

pyridine achieved a very good reaction record with a

rent methacrolein oxidation catalyst approximately

yield of 99%, 100,000 mol MMA/mol

Pd.27)

70% selectivity for methacrylic acid and methacrolein

A separation process combined with distillation that

could be achieved. One of the three equivalent methyl

includes an amount of ethylene of several percent in a

groups on isobutane is kept, another methyl group is

naphtha cracker C3 stream for the raw material propy-

dehydrogenated, while the third is carboxylated. It can

ne (and propadiene), extraction and isomerization of

occur on the same catalyst, even though it is surpris-

propadiene, was developed, but even at a 1,000,000

ing for a high level chemical reaction. At present this

t/year ethylene center, there will only be 40,000

has not reached a catalytic performance level that

50,000 t/y of MMA, and the major limiting condition is

makes commercialization possible, and it is thought

the problem of raw materials. At present, this process

that a practical application will take just a little more

technology has been assigned to ICI by Shell and can

time.

be thought of as belonging to Lucite, but it seems that

they have no will to commercialize it now.

As a part of the NEDO Simple Chemistry Project, we

are participating in the development of saturated hydro-

Moreover, there is also the isobutyric acid process

carbon selective oxidation reaction technology, and

among the methods that were actively researched in

since reaction mechanisms have been examined and

the past for processes using C 3 as a raw material.

processes evaluated, an outline is given below.32) 35)

Isobutyric acid is synthesized by means of an HF cata-

The catalyst used is a heteropolyacid catalyst formed

lyst from propylene and CO, and methacrylic acid is

from Mo-P-V-As-Cu, which has exhibited a good record

derived by oxidative dehydrogenation. The perfor-

in current methacrolein oxidation. Fig. 6 shows a typi-

mance of the later step catalyst is insufficient, and it

cal reaction performance. If the conversion rate is high,

has been abandoned.

the selectivity suddenly falls, and a yield of only about

10% is obtained.35)
Fig. 7 shows the reaction paths that can be consid-

3. Isobutane Process

ered. Isobutylene is the first intermediate, and it has

been confirmed that this is the rate-limiting step. Table
O2
Mo-P

O
OH

CH3OH
acid

SUMITOMO KAGAKU 2004-II

O
O

4 shows the rate constants for each step.34) It is known

that the isobutylene formed by dehydrogenation pro-

60

Selectivity

0.4

40
0.2

20

Conversion
0.0
570

590

610

630

650

2.5
150
2.0
100

1.5
1.0

50
0.5
0.0

0
0

670

200

3.0

50

100

150

200

250

300

Total pressure /kPa

Temperature /K

Typical reaction performance. ( ) productivity of MAL+MAA, ( ) conversion of isobutane, and ( ) selectivity to MAL+MAA.
Feed composition: [isobutane]=25 vol.%,
[O2]=25 vol.%, [H2O]=15 vol.%, [N2]=balance. Operating conditions: SV=1000
ml g1 h1, P=150 kPa, Contact time=5.4 s.

Fig. 6

iC4 partial pressure /kPa

Productivity/mmol h1 gcat1

80

0.6

Select. or Conv./%

100

0.8

Productivity/mmol h1 gcat1

Trends and Future of Monomer-MMA Technologies

Fig. 8

Influence of the total pressure, at constant

P/SV ratio=0.1, on (
) productivity of
MAL+MAA, and (
) isobutane partial
pressure. Feed composition: [isobutane]=37 vol.%, [O2]=37 vol.%, [H2O]=15
vol.%, [N2]=balance. Operating conditions:
SV=10002700 ml g1 h1, P=100270 kPa,
T=623 K, Contact time=3.5 s.

iC4

tane, thus even if the conversion is low, if the isobutane

concentration and the pressure are increased, this
k1

k1

process can be taken to a level that is not inferior to the

MAA

isobutylene direct oxidation method, in terms of MAA

O
O k4

k2

iC4

OH
CO,CO2

dency of productivity.35)

OH
k3

Based on this reactivity, we have proposed a recy-

k2

k3

cling process as shown in Fig. 9, and estimated the

O

material balance, energy budget and the like. Table 5

MAL

Fig. 7

productivity. Fig. 8 shows data on the pressure depen-

gives the results of a comparison with the direct oxida-

Scheme of isobutane selective oxidation

reaction.

tion process.32) The recycling yield is approximately

52%, but the part going to the combustion reaction can
be recovered as energy (steam). Assuming that

Table 4

Kinetic parameters of isobutane oxidation

reaction on Mo-P-V-As-Cu-Cs heteropolyacid catalyst.
Eax/kJ mol1

kx/s1

kx/s1

isobutylene is synthesized by the isobutane dehydrogenation process (the UOP Oleflex process, 36) for
example), calculating only the energy invested, we get

kx/(kx + kx)

( at 573K) (at 573K)

iC4 (x=1)

84.3

0.0084

0.0015

0.85

iC4 (x=2)

57.0

4.10

1.03

0.8

60.5

1.16

0.06

0.95

MAL (x=3)
MAA (x=4)

135

0.0185

Incinerator
i-C4
Steam

H2O

d[iC4]/dt = (k1+k1)[iC4]
d[iC4]/dt = k1[iC4] (k2 + k2)[iC4]
d[MAL]/dt = k2[iC4] (k3 + k3)[MAL]
d[MAA]/dt = k3[MAL] k4[MAA]

Air, O2
to Extraction

gresses to methacrylic acid comparatively rapidly and

with high selectivity, but the target MAA is oxidized at

iC4, MAL, Air

Reactor

a rate twice that of the isobutane reaction, causing the

selectivity to drop. However, it is known that the MAA
combustion is inhibited by the coexistence of isobu-

SUMITOMO KAGAKU 2004-II

Fig. 9

iC4,MAL Absorber
Scrubber

iC4,MAL Stripper

Supposed isobutane direct oxidation

process.

10

Trends and Future of Monomer-MMA Technologies

Table 5

Comparison of isobutane process with isobutylene direct oxidation process.

Isobutane direct oxidation process

Isobutylene direct oxidation process

Reaction performance

Reaction performance
100%

iC4 conv.

65%

MAA yield

iC4 conv.

10%

(Recycle conv.)

96%

MAA select.

50%
5%

MAL select.

52%

(Recycle MAA yield)

Unit consumption
/tMMA

as Fuel/t

$/t

Unit consumption
/tMMA
iC4

iC4

0.86 t

0.991

310

Power

500 kWh

0.10

40

Power

650 kWh

0.06

12

Steam

4.5 t

93%O2

1160 Nm3

1 t

Steam
Sum

1.03

338

Supposed unit price

1.124 t

Sum

as Fuel/t

$/t

1.12

270

0.13

52

0.28

54

0.09

34

1.06

302

per 1ton fuel

C4LPG

200 $/t

Power

Isobutylene

360 $/t

Steam

Isobutane

240 $/t

93%O2

0.08 $/kWh
12 $/t
0.37 kWh/Nm3

Power

5000 kWh

Steam

16 t

(Heat

46 GJ)

a value equivalent to 1.15 times the isobutane. This

and it seems that the C4 processes will play a leading

isobutane method requires oxygen enriched air, and

role in the near future. The process for obtaining MAA

energy is necessary for applying pressure and recy-

in air oxidation using an unmodified branched C4 struc-

cling, so with the current catalyst performance it does

ture should be reasonable. There is a need to follow

not reach the isobutylene process in terms of energy

the future trends in the direct oxidative esterification

by a small margin. If isobutylene is produced from

process and alpha process. However, in order to nur-

isobutane, the price cannot be 1.15 times, and if the

ture the direct oxidation process, Sumitomo Chemical

price of isobutylene is as shown in Table 5, calculations

/ Nippon Shokubai method, as the most competitive

of the variable cost advantage of the isobutane process

MMA technology, we should continue improving the

can be established with these figures. However,

catalytic performance. In particular, concerning the

isobutylene is currently valued as a byproduct of ethyl-

second step heteropolyacid catalyst in the tandem

ene, cracked gasoline and the like. On the other hand,

process, a catalyst resistant to isobutylene poisoning is

C4LPG, which is the raw material for isobutane, is val-

required. In addition, the development of a catalyst

ued independently from naphtha for trading, so the situ-

with high selectivity that controls the overoxidation of

ation is such that isobutane cannot always be called

methacrylic acid is desired. This is the direction of the

advantageous. It is also necessary to surpass the pre-

development of isobutane process catalysts. Increasing

sent methods in terms of energy consumption, and the

the performance of current catalysts can be thought of

development of a higher performance catalyst is the key

as being directly connected to the development of cata-

to the realization of this process. The direction of the

lysts for the isobutane process, which is the technology

future improvement of the catalyst that came to the sur-

for the future.

face from the investigation of the reaction mechanism is

moving to a catalyst that has strong durability for the

References

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PROFILE

Koichi N AGAI

Toshiaki U I

Sumitomo Chemical Co., Ltd.

Basic Chemicals Research Laboratory
Senior Research Associate

Sumitomo Chemical Co., Ltd.

Basic Chemicals Research Laboratory
Senior Research Associate

SUMITOMO KAGAKU 2004-II

12